Phosphoric acid pretreatment enhances the specific surface areas of biochars by generation of micropores

Highlights: • Phosphoric acid treatment enhances surface area due to the generated micropores. • Cellulose produces more micropores than lignin after phosphoric acid treatment. • Acid catalysis and crosslinking contribute to micropore generation. • Large surface area and pore volume of the treated biochars enhanced the sorption. • Phosphoric acid modified biochars could be applied in P-depleted soil. Biochars are being increasingly applied in soil for carbon sequestration, fertility improvement, as well as contamination remediation. Phosphoric acid (H₃PO₄) pretreatment is a method for biochar modification, but the mechanism is not yet fully understood. In this work, biochars and the raw biomass were treated by H₃PO₄ prior to pyrolysis. Due to an acid catalysis and crosslink, the micropores of the pretreated particles were much more than those without H₃PO₄ pretreatment, resulting in the dramatical enhancement of specific surface areas of the pretreated particles. Crystalline cellulose (CL) exhibited a greater advantage in the formation of micropores than of amorphous lignin (LG) with H₃PO₄ modification. The formation mechanisms of micropores were: (a) H⁺ from H₃PO₄ contributes to micropores generation via H⁺ catalysis process; (b) the organic phosphate bridge protected the carbon skeleton from micropore collapse via the crosslinking of phosphate radical. The sorption capacities to carbamazepine (CBZ) and bisphenol A (BPA) increased after H₃PO₄ modification, which is ascribed to the large hydrophobic surface areas and more abundant micropores. Overall, H₃PO₄ pretreatment produced biochars with large surface area and high abundance of porous structures. Furthermore, the H₃PO₄ modified biochars can be applied as high adsorbing material as well as P-rich fertilizer.